EP0204442B1 - Préparation de copolymères - Google Patents

Préparation de copolymères Download PDF

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Publication number
EP0204442B1
EP0204442B1 EP86303558A EP86303558A EP0204442B1 EP 0204442 B1 EP0204442 B1 EP 0204442B1 EP 86303558 A EP86303558 A EP 86303558A EP 86303558 A EP86303558 A EP 86303558A EP 0204442 B1 EP0204442 B1 EP 0204442B1
Authority
EP
European Patent Office
Prior art keywords
phb
alcaligenes eutrophus
strain
accumulating
utilising
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP86303558A
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German (de)
English (en)
Other versions
EP0204442A2 (fr
EP0204442A3 (en
Inventor
Peter James Senior
Stephn Hugh Collins
Kenneth Raymond Richardson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Monsanto Co
Original Assignee
Imperial Chemical Industries Ltd
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Filing date
Publication date
Application filed by Imperial Chemical Industries Ltd filed Critical Imperial Chemical Industries Ltd
Priority to AT86303558T priority Critical patent/ATE69267T1/de
Publication of EP0204442A2 publication Critical patent/EP0204442A2/fr
Publication of EP0204442A3 publication Critical patent/EP0204442A3/en
Application granted granted Critical
Publication of EP0204442B1 publication Critical patent/EP0204442B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/62—Carboxylic acid esters
    • C12P7/625—Polyesters of hydroxy carboxylic acids

Definitions

  • the present invention relates to a process of producing copolymers and in particular to a process of producing copolymers of 6-hydroxybutyric acid and S-hydroxyvaleric acids.
  • poly 6-hydroxybutyric acid is referred to as PHB
  • poly 8-hydroxyvaleric acid is referred to as PHV.
  • the present invention relates to the production of PHB/PHV copolymers.
  • PHB is a thermoplastic polyester comprising repeat units of the formula:
  • micro-organisms which is accumulated by many micro-organisms, particularly bacteria, for example of the genera Alcaligenes, Athiorhodium, Azotobacter, Bacillus, Nocardia, Pseudomonas, Rhizobium and Spirillium, as an energy reserve material.
  • Poly 3-hydroxybutyric acid is conveniently prepared by cultivating the micro-organism in an aqueous medium on a suitable substrate, such as a carbohydrate or methanol, as an energy and carbon source.
  • a suitable substrate such as a carbohydrate or methanol
  • the substrate must, of course, be one that is assimilable by the micro-organism.
  • at least part of the cultivation is preferably conducted under conditions wherein there is a limitation of a nutrient that is essential for growth of the micro-organism but which is not required for polymer accumulation. Examples of suitable processes are described in EP-A-15669 and 46344 and USP 4336334 and 4433053.
  • PHB/PHV copolymers can be made by cultivating certain microorganisms such as Alcaligenes eutrophus using certain organic acids, for example propionic acid, or derivatives thereof such as salts or esters, as at least part of the substrate during at least part of the polymer accumulating stage of the cultivation.
  • certain microorganisms such as Alcaligenes eutrophus
  • organic acids for example propionic acid, or derivatives thereof such as salts or esters
  • PHB / PHV copolymers have a variety of uses in many fields of industry, for example see the article in Chemical Week, 28 August 1985, page 55 and in Manufacturing Chemist, October 1985, page 64.
  • Alcaligenes eutrophus does not normally utilise alcohols such as ethanol, see "The Prokaryotes" Chapter 70, p 882, ed M P Starr et al, published by Springer Verlag (1981). However by mutation and/or selection procedures it is possible to obtain ethanol utilising mutants or variants.
  • the present invention provides a process for producing a PHB-containing polymer comprising cultivating a PHB-accumulating strain of Alcaligenes eutrophus on a substrate under polymer-accumulating conditions such that the microorganism accumulates at least 10% by weight of the PHB-containing polymer characterised in that the PHB-accumulating strain of Alcaligenes eutrophus is also capable of utilising alcohol, and the PHB-containing polymer is a PHB/PHV copolymer, and that for at least part of the time when the microorganism is cultivated under polymer-accumulating conditions the substrate comprises at least one primary alcohol, other than methanol, having an odd number of carbon atoms.
  • Alcohol utilising strains of Alcaligenes eutrophus that can be used include the strain CBS 388.76 whose production is disclosed in USP 4138291 and strain NCIB 12080 which was deposited with the National Collection of Industrial Bacteria, Aberdeen on 2 May 1985.
  • the latter strain can be obtained from a glucose-utilising strain for example NCIB 11599 (deposited with the National Collection of Industrial Bacteria on 18 August 1980) that does not utilise ethanol, by cultivating the strain, for example NCIB 11599, in continuous culture under oxygen limitation on glucose as substrate and then, transferring to carbon limitation on a substrate containing a mixture of glucose and ethanol with progressive increase in the proportion of ethanol, relative to glucose, in the substrate until the substrate was wholly ethanol.
  • ethanol-utilising strains of Alcaligenes eutrophus are obtained by inducing the enzyme ethanol dehydrogenase. This is conveniently performed by limitation of the oxygen supply. Once the enzyme is induced exposure to ethanol in a continuous culture results in selection of an ethanol-utilising strain. The oxygen availability can be gradually increased to facilitate this selection.
  • polymer may also be accumulated while growth of the micro-organism is taking place: however, except in the case of micro-organisms that produce polymer constitutively, the amount of polymer so accumulated is generally small and typically is less than about 10% by weight of the cells produced. Although there can be a rise of polymer accumulation to about 30% by weight just before complete exhaustion.
  • the micro-organisms that do not produce polymer constitutively will grow, with little or no polymer accumulation, until one or more of the essential requirements for growth becomes nearly exhausted or exhausted, and then the micro-organism synthesises polymer.
  • the alcohol containing an odd number of carbon atoms as at least part of the substrate present during the period when copolymer is accumulated.
  • the odd numbered carbon atom alcohol will often be metabolised by the micro-organism by alternative pathways that do not give rise to copolymer: consequently in such cases copolymers will generally not be produced. Metabolism by such other pathways may also occur when using micro-organisms that accumulate copolymer constitutively.
  • the substrate in order to produce copolymers, contains a primary alcohol, other than methanol, containing an odd number of carbon atoms.
  • the alcohol is preferably heptan-1-oi, pentan-1-ol, or particularly, propan-1-ol. Mixtures of such alcohols may be employed.
  • the alcohol, or alcohols, having an odd number of carbon atoms may be used in admixture with another substrate assimilable by the micro-organism for example ethanol or a carbohydrate such as glucose.
  • the amount of combined carbon in the substrate as the alcohol or alcohols having an odd number of carbon atoms is at least 2%, preferably at least 10%, by weight of the total combined carbon in the substrate present during the period when the cultivation conditions are such that copolymer is being accumulated by the micro-organism.
  • the alcohol of alcohols having an odd number of carbon atoms form at least 25% by weight of the substrate employed during the copolymer accumulation stage.
  • various nutrient salts are required to enable the micro-organism to grow.
  • sources of the following elements in assimilable form normally as water soluble salts, are generally required: nitrogen, phosphorus, sulphur, potassium, sodium, magnesium, calcium, and iron, together with traces of elements such as manganese, zinc and copper.
  • sources of the following elements in assimilable form normally as water soluble salts, are generally required: nitrogen, phosphorus, sulphur, potassium, sodium, magnesium, calcium, and iron, together with traces of elements such as manganese, zinc and copper.
  • the most practical elements to limit are nitrogen, phosphorus, oxygen, or, less preferably, magnesium, sulphur or potassium. Of these it is most preferred to restrict the amount of nitrogen (which is conveniently supplied as an ammonium salt).
  • the amount of assimilable nitrogen required is about 8 - 15% by weight of the desired weight of cells less accumulated copolymer.
  • the fermentation is preferably conducted so that the dry weight of the copolymer-containing cells is at least 5 g per litre of aqueous medium.
  • the amount of the essential nutrient fed to the fermenter that is used to limit the amount of cell growth must be that required to support the growth of 6 g per litre of cells containing no copolymer: thus, if nitrogen is employed as the growth limiting nutrient, since the nitrogen content of copolymer free bacterial cells is about 8 - 15% by weight, the amount of assimilable nitrogen required would be between about 0.5 and 0.9 g per litre, e.g. about 0.6 to 1.2 g of ammonium ions per litre.
  • the fermentation may be conducted under the conditions e.g. pH, temperature, and degree of aeration (unless oxygen is utilised as the limiting nutrient) conventionally used for Alcaligenes eutrophus micro- organisms.
  • the amounts of nutrient salts (other than the growth limiting nutrient whose amount may be determined following the considerations outlined hereinbefore) employed may be those normally used for growth of the micro-organism.
  • the micro-organism is preferably grown to a certain desired weight by cultivation in the presence of sufficient of the nutrient required for growth that is to be restricted in the copolymer accumulation stage on a readily metabolisable substrate, such as a carbohydrate, and then cultivated under conditions of growth requirement restriction to cause the copolymer accumulation.
  • a readily metabolisable substrate such as a carbohydrate
  • the substrate for at least part, and in some cases all, of the growth stage may be the alcohol having an odd number of carbon atoms.
  • the fermentation may be performed as a batch fermentation in which case copolymer accumulation will occur as the amount of the nutrient that is required for growth but not for copolymer accumulation becomes depleted.
  • the fermentation may be conducted as a continuous process wherein aqueous medium containing the bacterial cells is removed, continuously or intermittently, from the fermentation vessel at a rate corresponding to the rate of addition of fresh aqueous medium and substrate thereto.
  • the amount of the nutrient that is restricted that is fed to the fermentation vessel is such that the aqueous medium removed from the vessel contains little or none of that nutrient, and the aqueous medium removed from the vessel is then fed to a second fermentation vessel, operated either in batch or, preferably, continuous fashion wherein copolymer accumulation is caused to take place by continuing the aerobic cultivation with the addition of a fresh quantity of substrate comprising the comonomer component. While additional quantities of substrate and nutrient salts may be added in this further fermentation step, since further growth is generally not desired, little or no further quantity of the nutrient utilised to limit growth should be added. It will however be appreciated that the aqueous medium fed to the further fermenter or fermenters from the first fermenter may contain some residual quantity of the limiting nutrient and/or the addition of a further small quantity thereof may be desireable for efficient operation.
  • the fermentation may be conducted as a single stage continuous process.
  • the residence time of the medium in the fermenter is made sufficiently long to allow the micro-organism to grow and exhaust the limiting nutrient supplied to the fermenter and to allow the micro-organism then to accumulate the copolymer.
  • the alcohol having an odd number of carbon atoms is used as part, or all, of the substrate during the copolymer accumulation stage occurring upon exhaustion of the nutrient required for growth.
  • the fermentation is preferably conducted so that the amount of accumulated copolymer comprises about 30 to 80% by weight of the bacterial cells.
  • the copolymer which generally has a molecular weight above 50,000 (weight average) and has the D(-) configuration, may be extracted from the micro-organism cells by a variety of techniques, for example those described in EP-A-15123.
  • Alcaligenes eutrophus variant NCIB 12080 was grown by continuous aerobic cultivation at pH 6.8 and 34°C in a 5 litre fermenter with a working volume of about 4 litres at a dilution rate (reciprocal of residence time) of 0.1 hr -1 .
  • the aqueous medium employed had the following composition, per litre of deionised water:
  • Iron and nitrogen were also continuously supplied, as aqueous solutions containing 11.5 g/l of nitrogen as ammonium hydroxide and 2 g/l ferrous sulphate heptahydrate acidified with sulphuric acid respectively, at such rates that the nitrogen and iron contents of the medium fed to the fermenter were 1040 mg/I and 7 mg/l respectively.
  • Ethanol and propan-1-ol were supplied at a rate of 12.1 and 12.6 gil respectively.
  • pH was controlled at 6.8 by the automatic addition of a 9:1 v/v mixture of 4 M potassium hydroxide and 4 M sodium hydroxide.
  • the cell dry weight of the effluent from the fermenter was 16.14 g.l and the cells contained 47% by weight of an PHB/PHV copolymer containing about 20 mol % PHV units and having a melting point of 133°C (as determined by differential scanning calorimetry).
  • the cell dry weight was 12.02 g/l and the cells contained 38% by weight of a polymeric product.
  • the polymeric product contained a higher overall PHV content than the polymer of Example 1 but was a complex product, exhibiting three distinct melting point peaks at 92.4°C, 110°C and 171°C. This is probably indicative that the polymer is a blend of a ⁇ -hydroxybutyrate homopolymer and one or more PHB/PHV copolymers.
  • NCIB 12080 Alcaligenes eutrophus NCIB 12080 was grown in a fed-batch technique under aerobic cultivation conditions at pH 6.8 and 34°C in a 5 litre fermenter. NCIB 12080 culture (80 ml) was inoculated into aqueous medium (3.4 I) of the following composition, per litre of de-ionised water:
  • the pH was controlled at 6.8 by the automatic addition of 50% vol/vol ammonium hydroxide solution.
  • the final cell dry weight was 33 gl- 1 and the cells contained 71% by weight of PHB/PHV polymer containing about 10% mol % hydroxyvalerate units. This had a melting point of 158°Cas determined by differential scanning calorimetry.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Zoology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Biotechnology (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (8)

1. Procédé pour la production d'un polymère contenant du PHB comprenant la culture d'une souche d'Alcaligenes eutrophus accumulant du PHB sur un substrat dans des conditions favorisant l'accumulation de polymère tel que le micro-organisme accumule au moins 10 % en poids du polymère contenant du PHB, caractérisé en ce que la souche d'Alcaligenes eutrophus accumulant du PHB est aussi capable d'utiliser un alcool et le polymère contenant du PHB est un copolymère de PHB/PHV, et que pendant au moins une partie du temps pendant lequel est cultivé le micro-organisme dans des conditions favorisant l'accumulation du polymère le substrat comprend au moins un alcool primaire autre que le méthanol, ayant un nombre impair d'atomes de carbone.
2. Procédé suivant la revendication 1, caractérisé en ce que l'alcool primaire est le propan-1-ol.
3. Procédé suivant l'une quelconque des revendications 1 ou 2, caractérisé en ce que l'alcool primaire fournit une teneur en carbone d'au moins 10 % en poids de la teneur en carbone totale du substrat présent pendant l'accumulation du polymère contenant du PHB.
4. Procédé suivant la revendication 3, caractérisé en ce que l'alcool primaire fournit une teneur en carbone d'au moins 25 % en poids de la teneur totale en carbone du substrat présent pendant l'accumulation du polymère contenant du pHB.
5. Procédé suivant l'une quelconque des revendications 1 à 4, caractérisé en ce que la souche accumulant du PHB d'Alcaligenes eutrophus est Alcaligenes eutrophus CBS 388.76 ou Alcaligenes eutrophus NCIB 12080.
6. Procédé suivant l'une quelconque des revendications 1 à 5, caractérisé en ce qu'il comprend dans une première étape, la culture de la souche d'Alcaligenes Eutrophus accumulant du PHB sur une source de carbone assimilable dans un milieu aqueux comprenant suffisamment d'une source d'azote assimilable pour entretenir une concentration d'au moins 5 g/1 d'un matériau cellulaire sans polymère contenant du PHB, et dans une seconde étape ultérieure, la culture de la souche d'Alcaligenes eutrophus accumulant du PHB dans des conditions de manque d'azote.
7. Alcaligenes eutrophus NCIB 12080 ou un mutant de celui-ci utilisant un alcool.
8. Procédé pour la préparation de la souche accumulant du PHB et de la souche utilisant un alcool d'Alcaligenes eutrophus suivant la revendication 1 à partir d'une souche d'Alcaligenes eutrophus utilisant du glucose, caractérisé en ce que la souche d'Alcaligenes eutrophus utilisant du glucose est cultivée sous limitation d'oxygène pour enduire l'enzyme éthanol déshydrogénase, et qu'ensuite la souche d'Alcaligenes eutrophus utilisant du glucose est cultivée sur un substrat comprenant du glucose et une proportion d'éthanol augmentant progressivement pour produire ainsi des mutants qui sont capables d'utiliser un alcool.
EP86303558A 1985-05-28 1986-05-09 Préparation de copolymères Expired - Lifetime EP0204442B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86303558T ATE69267T1 (de) 1985-05-28 1986-05-09 Copolymerherstellung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB858513310A GB8513310D0 (en) 1985-05-28 1985-05-28 Copolymer production
GB8513310 1985-05-28

Publications (3)

Publication Number Publication Date
EP0204442A2 EP0204442A2 (fr) 1986-12-10
EP0204442A3 EP0204442A3 (en) 1987-10-07
EP0204442B1 true EP0204442B1 (fr) 1991-11-06

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EP86303558A Expired - Lifetime EP0204442B1 (fr) 1985-05-28 1986-05-09 Préparation de copolymères

Country Status (11)

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EP (1) EP0204442B1 (fr)
JP (1) JPH0779705B2 (fr)
AT (1) ATE69267T1 (fr)
AU (1) AU601681B2 (fr)
BR (1) BR8602397A (fr)
CA (1) CA1313635C (fr)
DE (1) DE3682328D1 (fr)
GB (2) GB8513310D0 (fr)
IN (1) IN167933B (fr)
NZ (1) NZ216268A (fr)
ZA (1) ZA863661B (fr)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0288908B1 (fr) * 1987-04-28 1992-10-21 Mitsubishi Gas Chemical Company, Inc. Procédé pour la production d'un copolymère statistique contenant des unités de D-(-)-3-hydroxybutyrate et de D-(-)-3-hydroxyvalérate
US5245023A (en) 1987-06-29 1993-09-14 Massachusetts Institute Of Technology Method for producing novel polyester biopolymers
US4876331A (en) * 1987-08-18 1989-10-24 Mitsubishi Kasei Corporation Copolyester and process for producing the same
EP0396289B1 (fr) * 1989-05-02 1995-10-25 Zeneca Limited Production de copolymères
US5264546A (en) * 1989-05-02 1993-11-23 Imperial Chemical Industries Plc Copolymer production
US5371002A (en) * 1989-06-07 1994-12-06 James Madison University Method of production of poly-beta-hydroxyalkanoate copolymers
GB8927794D0 (en) * 1989-12-08 1990-02-14 Ici Plc Copolymer production
WO1991013207A1 (fr) * 1990-02-21 1991-09-05 Pulp And Paper Research Institute Of Canada POLY-β-HYDROXYALCANOATES UTILISES DANS LES ASSEMBLAGES DE FIBRES ET LES FILMS
US5451456A (en) * 1990-02-21 1995-09-19 Pulp And Paper Research Institute Of Canada Latex of poly-β-hydroxyalkanoates for treating fiber constructs and coating paper
GB9011777D0 (en) * 1990-05-25 1990-07-18 Ici Plc Hv/hb copolymer production
US5200332A (en) * 1990-09-14 1993-04-06 Mitsubishi Gas Chemical Company, Inc. Process for preparation of copolymer
AT395319B (de) * 1990-10-05 1992-11-25 Danubia Petrochem Polymere Verfahren zur gewinnung eines polyhydroxyalkanoates aus dem zellmaterial eines mikroorganismus und polyhydroxyalkanoatflocken
US5569595A (en) * 1991-09-27 1996-10-29 Center For Innovative Technology Production of poly-β-hydroxybutyrate in prokaryotic host cells
DE4433134A1 (de) * 1994-09-16 1996-03-21 Buck Chem Tech Werke Verfahren zur Herstellung von Polyhydroxyfettsäuren sowie rekombinanter Bakterienstämme zur Durchführung des Verfahrens
NL1011431C2 (nl) * 1999-03-03 2000-09-05 Univ Delft Tech Werkwijze voor het produceren van polyhydroxyalkanoaat.
MY136899A (en) 2002-10-10 2008-11-28 Kaneka Corp Method for producing copolyester
EP2284261B1 (fr) 2008-04-23 2017-03-29 Toyota Jidosha Kabushiki Kaisha Procédé de production d un copolymère de polyester à l'aide d un micro-organisme génétiquement modifié
EP2377945B1 (fr) 2008-10-27 2015-09-02 Toyota Jidosha Kabushiki Kaisha Méthode pour la fabrication de polylactate à l'aide d'une microorganisme récombinante

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3063405D1 (en) * 1979-02-21 1983-07-07 Ici Plc Microbiological process for the production of poly (beta-hydroxybutyric acid) and micro-organisms for use therein
AU560653B2 (en) * 1981-07-07 1987-04-16 Monsanto Company 3-hydroxybutyrate polymers
GB8301344D0 (en) * 1983-01-18 1983-02-16 Ici Plc Poly(beta-hydroxybutyric acid)
GB8311677D0 (en) * 1983-04-28 1983-06-02 Ici Plc Extraction process
DE3343551A1 (de) * 1983-12-01 1985-06-13 Lentia GmbH Chem. u. pharm. Erzeugnisse - Industriebedarf, 8000 München Verfahren zur biotechnologischen herstellung von poly-d(-)-3-hydroxybuttersaeure

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CA1313635C (fr) 1993-02-16
AU5782586A (en) 1986-12-04
EP0204442A2 (fr) 1986-12-10
BR8602397A (pt) 1987-01-21
GB8611523D0 (en) 1986-06-18
ATE69267T1 (de) 1991-11-15
DE3682328D1 (de) 1991-12-12
JPH0779705B2 (ja) 1995-08-30
EP0204442A3 (en) 1987-10-07
IN167933B (fr) 1991-01-12
GB8513310D0 (en) 1985-07-03
NZ216268A (en) 1989-04-26
ZA863661B (en) 1987-02-25
AU601681B2 (en) 1990-09-20
JPS61293385A (ja) 1986-12-24

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